三嗪类化合物的合成及其产酸性能研究

合成了一系列的三嗪类光生酸剂1a-1e，确定了它们的结构，并对1e在乙腈溶剂中365和405nm光下的曝光分解产酸性能进行了初步的定量研究．结果表明，在测定浓度范围内分解量子产率和产酸量子产率基本上都不随浓度的变化而变化，在405nm光下比在365nm光下有更高的分解和产酸量子效率．有关这类化合物的光生酸性能与曝光波长的关系正在进一步研究中．     

三嗪类光生酸剂的产酸性能研究

采用UV-vis光谱分析的方法,选用罗丹明B为酸示踪剂,对4种新合成的三嗪类光生酸剂(PAG1 -PAG4),分别在405nm和365nm下乙腈中的分解及产酸性能进行了研究,推导计算得到了其分解及产酸量子产率,并对这4种化合物的产酸量子产率进行了比较。实验结果表明405nm光源下4种三嗪光生酸剂中2-(9-葸乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪(PAG4)的分解和产酸量子产率达到分别为10%,9%,为四者中最高的;2-(4-羟基-1-苯乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪(PAG2)几乎不分解也不产酸;而在365nm光源下4种光生酸剂的分解及产酸量子产率均很低。     

新型紫外光产酸剂的合成及其光聚合动力学研究

以2-硝基噻吩,甲基磺酰氯及苯乙腈为原料合成了一种紫外光产酸剂(5-甲磺酸酯亚胺-5H-噻吩-2-亚基)-苯基-乙腈(MTPA),通过傅里叶红外光谱仪、核磁共振仪和紫外吸收光谱仪及热重分析对所合成的产物的结构和性能进行了表征,并利用实时红外(RT-IR)对该引发剂进行了光聚合反应动力学研究。考察了单体、产酸剂浓度对引发速率及单体转化率的影响。结果表明,在一定浓度范围内,随着引发剂浓度增大,聚合速率加快,最终的双键转化率也增高。     

钒酸铋的制备及可见光降解罗丹明B的研究

以偏钒酸铵和碳酸铋为原料,用NaOH调节体系pH,水热法合成钒酸铋（BiVO₄）光催化剂。利用XRD和UV-Vis漫反射对样品的晶型结构和光吸收特性进行表征分析。以罗丹明B为目标降解物,卤素灯（λ＞400 nm）为光源,探讨水热温度、水热时间对合成BiVO₄催化剂的可见光催化活性影响。结果表明,在水热温度为200 ℃、水热时间为8 h的条件下合成的钒酸铋光解效率最高。实验还研究了罗丹明B水溶液pH、催化剂投加量对光催化罗丹明B降解率的影响。结果表明,在罗丹明B水溶液pH为3、初始质量浓度为10 mg/L、每60 mL溶液催化剂投加量为0.4 g时能达到较好的光催化效果,反应2 h后降解率可达97%。     

一种基于三苯胺类光生酸剂的制备与表征

成功合成了1种以三苯胺为主体的硫盐光生酸剂,其结构经1HNMR、IR分析确证,并对其物性进行了基本考察,有较高的热分解温度和在常用有机溶剂中有较好的溶解性。并考察了其在相同浓度、相同光强、相同曝光波长(405 nm)下在3种不同溶剂(乙腈、四氢呋喃、二氯甲烷)中的分解及产酸性能,计算出分解量子产率和产酸效率。     

新型钒氧簇合物(BiVO_4)的光催化性能研究

钒氧簇合物作为一类同多酸类的化合物,很可能具有一些光催化性质。本文以硝酸铋、偏钒酸铵为原料,采用水热合成法制备了钒酸铋;以可见光光催化解罗丹明B作为模型反应,详细考察了合成条件(模板剂种类、陈化时间、晶化温度),并采用X-射线粉末衍射(XRD)、傅立叶变换红外(FT-IR)、拉曼光谱(Raman)和紫外-可见漫反射(UV-Vis-DRS)等手段对样品的理化性能进行了详细表征。结果表明:BiVO4的最佳合成条件是以四丙基氢氧化铵为模板剂,陈化时间为1d,晶化温度为170℃;在可见光下对罗丹明B具有良好的光催化性能,辐照5h,罗丹明B溶液的脱色率可达90.6%。     

原甲酸三乙酯法合成巴比妥酸衍生物的研究

本实验利用原甲酸三乙酯与巴比妥酸及尿素反应合成了巴比妥酸5位被取代的衍生物。通过考察反应物物质的量的比,反应溶剂,反应温度变化对产品产量的影响,找到最佳的反应条件。通过~1H NMR核磁共振确定氢原子的位置和红外光谱确定该物质所具有的官能团并进一步测定化合物的紫外光谱和荧光光谱。化合物在紫外-可见光波长范围内有三个吸收峰,在紫外吸收剂方面有潜在的应用价值。     

一种新型酞菁类光蚀刻记录材料的光生酸性质研究

通过研究对甲苯磺酸酯空心酞菁的性质，发现该化合物在紫外光照射下可生酸，是一种光生酸剂．由于酞菁类化合物本身具有光催化氧化反应的性能，因此这类光生酸剂在光蚀刻技术中将有很好的应用潜能．     

流感疫苗中裂解剂TritonN-101残余量的快速检测方法

目的快速、准确地检测流感病毒裂解疫苗和亚单位疫苗中裂解剂Triton N-101的残余量。方法采用紫外吸收与Lowry蛋白测定相结合的方法。首先绘制裂解剂和蛋白标准曲线,将Lowry法测得的样品蛋白质含量代入蛋白标准曲线的回归方程中,得出样品中蛋白对应的紫外吸收值,再用蛋白样品测得紫外吸收值减去蛋白吸收值的差,代入裂解剂标准曲线,得出裂解剂浓度,并对该法进行精密度和准确度验证。结果经精密度和准确度的验证,该法符合实验要求。结论所采用的方法快速、简便,适用于疫苗生产过程中裂解剂Triton N-101残余量的检测。     

银修饰钒酸铋的制备及其催化性能研究

将低温水热法制备的单斜晶型BiVO_4作为载体,采用光还原法获得催化活性提升的Ag/BiVO_4复合材料。通过X射线衍射(XRD)、X射线能谱(EDX)、紫外可见漫反射(UV-DRS)表征方法检测Ag/BiVO_4材料的组成和光学性质,测试了Ag/BiVO_4在可见光照射条件下对罗丹明B(Rh B)的降解性能。结果表明,10 at%Ag/BiVO_4复合材料表现出最佳的光催化活性。本工作合成条件温和、步骤简便,并对银负载钒酸铋光催化剂的催化活性机理进行讨论。     

Photoacid generators for catalytic decomposition of polycarbonate

The photo‐activated, acid catalyzed decomposition of polycarbonate was investigated in this study. The impact of the chemical and physical properties of the photoacid generators (PAG) and the ambient atmosphere effect on polycarbonate decomposition were discussed. The photo‐patterns resulted from the photoacid catalyzed decomposition of a polycarbonate can be used as a sacrificial placeholder for fabrication of microelectromechanical and microfluidic devices. The effects of acid strength, vapor pressure of the acid, PAG activation process, and ambient conditions (temperature, moisture, and oxygen concentrations) on polymer film decomposition were studied. Several superacids (e.g. triflic and nonaflic based PAGs) were not suitable for decomposition of the polycarbonate because of their high vapor pressures resulting in the high volatility properties. From the decomposition experiments it was found that the nonfluorinated sulfonic acid based PAGs do not posses the superacidity needed for decomposition. Perfluorinated methide and a tetrakis (pentafluoropheyl)borate PAG were effective in the decomposition of polycarbonate films. The combination of two PAGs, one which generates high vapor pressure acid (thus, highly volatile) and the other with a lower vapor pressure acid (thus, less volatile) showed very low residue levels. This is because of the volatility of the generated high vapor pressure acid (usually remaining acid in the film was the cause of the residue left behind) and the remaining nonvolatile low vapor pressure acid was sufficient to decompose the polycarbonate that was not decomposed by the generated high volatile acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

固相萃取-HPLC法测定指甲油中的罗丹明B

建立了固相萃取-HPLC法测定指甲油中罗丹明B的方法.指甲油经中性氧化铝固相萃取小柱富集、净化后,以丙酮-正己烷溶液洗脱,用紫外检测器检测,使用TopsilTM-C18色谱柱,75％甲醇水溶液作流动相,检测波长为554 nm.当进样浓度在0.5～25 μg/mL范围内,线性关系良好,R2=0.9999,加标回收率为90.1％～94.0％,检测限为0.06 μg/mL.     

Changes of fluorescence color in novel poly(azomethine) by the acidity variation

A novel polymer, poly(4,4′‐oxydiphenylenemethylidynenitrilo‐2,5‐dihexyloxy‐1,4‐phenylenenitrilomethyli‐ dyne) (POPNM), with a azomethine structure, containing long alkoxy side chains, was synthesized by the polycondensation of 2,5‐bis(hexyloxy)terephthalaldehyde with 4,4′‐oxydianiline. It displayed acid‐sensory properties as colorimetric and fluorescent transducers to the strong acid analytes because of the protonation of an imine group in the compound. To examine the sensitivity to the acid, the effect of absorption and fluorescence of the polymer was investigated by simply adding trifluoroacetic acid into a chloroform solution of the polymer, and as a result, the multiple colors of fluorescence were sharply changed. Increasing the amount of the acid, the maximum absorption bands of fluorescence spectra were bathochromically shifted from 470 to 570 nm and, then, treating the pyridine as a base, they were recovered. A polymer film containing both the polymer and a photoacid generator (PAG) was prepared by semi‐interpenetrating network polymerization method. When the polymer film was exposed to UV in the presence of PAG through a photomask, well‐resolved fluorescent image patterns were readily obtained. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1228–1233, 2006     

Exclusion chromatography using porous glass. II. Application to hydrophilic polymers

A chromatograph employing five columns packed with porous glass of pore size 1250 Å to 75 Å provided peak retention volumes (V_R) that were reproducible and essentially independent of sample size and flow rate when aqueous eluents were used. Calibration was carried out with a series of dextran fractions and polystyrene sulfonate samples, both of moderately narrow molecular weight distribution. The universal calibration method, based on hydrodynamic volume, was tested for four different polymer types. All four types produced a common curve within experimental error, which indicates that absolute molecular weight distributions may be derived from aqueous exclusion chromatography data for at least these polymer types. Additional study using a higher salt concentration produced hydrodynamic-volume plots that superposed with those above. The use of the same set of porous glass columns with polystyrene standards in three different organic solvents produced calibration curves that agreed well with the aqueous curves after corrections were made for differences in available pore volumes.     

Triphenylsulfonium salt methacrylate bound polymer resist for electron beam lithography

A new photoacid generator (PAG) bound polymer containing triphenylsulfonium salt methacrylate (TPSMA) was synthesized and characterized. The PAG bound polymer was employed to improve electron beam lithographic performance, including sensitivity and resolution. The PAG bound polymer resist exhibited a higher sensitivity (120 μC/cm²) than the PAG blend polymer resist (300 μC/cm²). Eliminating the post exposure baking process during development improved the resolution due to decreased acid diffusion. A high-resolution pattern fabricated by electron beam lithography had a line width of 15 nm and a high aspect ratio. The newly developed patterns functioned well as masks for transferring patterns on Si substrates by reactive ion etching.     

Gel Permeation Chromatography Calibration. I. Use of Calibration Curves Based on Polystyrene in THF and Integral Distribution Curves of Elution Volume to Generate Calibration Curves for Polymers in 2,2,2-Trifluoroethanol

Abstract

A general method is proposed for obtaining gel permeation chromato-graphic (GPC) molecular weight (MW) and hydrodynamic volume (HDV) calibration curves for polymer-solvent systems where primary polymer standards are unavailable. The method is demonstrated by using a HDV calibration curve based on polystyrene in tetrahydrofuran (THF), in conjunction with integral distribution curves of elution volume for poly(methyl methacrylate) (PMMA) in THF and in 2,2,2-tri-fluoroethanol (TFE) for the generation of a HDV calibration curve in TFE. Transformation methods for generating secondary MW calibration curves from HDV calibration curves are discussed and applied to PMMA in THF and TFE, and to poly(trimethylene oxide), poly(vinyl acetate), and certain polyamides in TFE. The utility and reliability of the secondary calibration curves are demonstrated by comparing MW average and intrinsic viscosites obtained by GPC and by the classical methods. Molecular structural differences among th polyamide samples associated with the distribution of short- and long-chain branches are discussed in relation to their secondary calibration curves.     

Molecular diffusion in ternary poly(vinyl alcohol) solutions

The diffusion kinetics of a molecular probe—rhodamine B—in ternary aqueous solutions containing poly(vinyl alcohol), glycerol, and surfactants was investigated using fluorescence correlation spectroscopy and dynamic light scattering. We show that the diffusion characteristics of rhodamine B in such complex systems is determined by a synergistic effect of molecular crowding and intermolecular interactions between chemical species. The presence of glycerol has no noticeable impact on rhodamine B diffusion at low concentration, but significantly slows down the diffusion of rhodamine B above 3.9% (w/v) due to a dominating steric inhibition effect. Furthermore, introducing surfactants (cationic/nonionic/anionic) to the system results in a decreased diffusion coefficient of the molecular probe. In solutions containing nonionic surfactant, this can be explained by an increased crowding effect. For ternary poly(vinyl alcohol) solutions containing cationic or anionic surfactant, surfactant–polymer and surfactant–rhodamine B interactions alongside the crowding effect of the molecules slow down the overall diffusivity of rhodamine B. The results advance our insight of molecular migration in a broad range of industrial complex formulations that incorporate multiple compounds, and highlight the importance of selecting the appropriate additives and surfactants in formulated products.     

Upgrading poly(styrene-co-divinylbenzene) beads: Incorporation of organomodified metal-free semiconductor graphitic carbon nitride through suspension photopolymerization to generate photoactive resins

The inclusion of the metal free semiconductor graphitic carbon nitride (g-CN) into polymer systems brings a variety of new options, for instance as a heterogeneous photoredox polymer initiator. In this context, we present here the decoration of the inner surface of poly(styrene-co-divinylbenzene) beads with organomodified g-CN via one pot suspension photopolymerization. The resulting beads are varied by changing reaction parameters, such as, crosslinking ratio, presence of porogens, and mechanical agitation. The photocatalytic activity of so-formed beads was tested by aqueous rhodamine B dye photodegradation experiments. Additionally, dye adsorption/desorption properties were examined in aqueous as well as in organic solvents. Photoinduced surface modification with vinylsulfonic acid and 4-vinyl pyridine is introduced. Overall, metal-free semiconductor g-CN donates photoactivity to polymer networks that can be employed for dye photodegradation and acid–base catalyst transformation through facile photoinduced surface modifications.     

Polymer concentration detection method based on fluorescent polymer to evaluate its retention and percolation

A new fluorescent polymer was prepared by copolymerization of acrylamide and a modified rhodamine B (RhB). Fourier transformation infrared spectrometer and nuclear magnetic resonance confirmed the successful modification of RhB and the synthesis of fluorescent polymer. The rheological and fluorescence properties were studied by fluorospectrophotometer and rotational rheometer. The adsorption retention and percolation properties were evaluated by sand pack displacement experiments. The results indicated that fluorescence intensity revealed a distinct linear relationship with polymer concentration within a certain concentration range. High temperature and strong acidic conditions could diminish fluorescence intensity whereas formation water ions exerted inconsiderable influence on it. Rheological results manifested that fluorescent polymer can be used as polymer flooding agent. The sand pack displacement results proved the feasibility of using fluorescent polymer to detect polymer concentration. By this means, polymer breakthrough time and concentration variations could be confirmed. Based on the curves of injection pressure and polymer concentration, the percolation state and retention of polymer were able to be analyzed. Significantly, this work can provide support and guidance for the practical applications of fluorescent polymer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47468.     

A single component photoimaging system with styrene copolymers having t-BOC-protected quinizarin dye precursors and photoacid generating groups in a single polymer chain

A styrene monomer tBQSt, having a tert-butyloxycarbonyloxy (t-BOC)-protected quinizarin dye precursor as a pendent, has been copolymerized with N-(tosyloxy)maleimide (TsOMI) to obtain a dual functional polymer P(tBQSt/TsOMI). The polymer P(tBQSt/TsOMI), as a single component photoimaging system without using an external photoacid generator (PAG), was applied for fluorescent photopatterning by dry process based on the chemical amplification (CA) process. The TsOMI units in the polymer chains were responsible for photochemical generation of p-toluenesulfonic acid by UV exposure and the acid generated in the solution cast polymer film induced the catalytic deprotection of acid labile t-BOC groups of the quinizarin dye precursors. Accordingly, the quinizarin moieties were regenerated in the polymer chains by the CA process, thereby recovering the original color and fluorescence of the quinizarin dye. Fluorescent patterns were readily delineated on the thin polymer films by imagewise UV exposure even without a wet development process.